Metal−organic molecule−semiconductor junctions are controlled not only by the molecular properties, as in metal−organic molecule−metal junctions, but also by effects of the molecular dipole, the dipolar molecule−semiconductor link, and molecule−semiconductor charge transfer, and by the effects of all these on the semiconductor depletion layer (i.e., on the internal semiconductor barrier to charge transport). Here, we report on and compare the electrical properties (current−voltage, capacitance−voltage, and work function) of large area Hg/organic monolayer-Si junctions with alkyl and alkenyl monolayers on moderately and highly doped n-Si, and combine the experimental data with simulations of charge transport and electronic structure calculations. We show that, for moderately doped Si, the internal semiconductor barrier completely controls transport and the attached molecules influence the transport of such junctions only in that they drive the Si into inversion. The resulting minority carrier-controlled ju...
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